2-oxodihydroquinolinethiono-phosphoric (phosphonic) acid esters

ABSTRACT

2-Oxodihydroquinolinethiono-phosphoric (-phosphonic) acid esters, i.e., O,O-dialkyl-(1-methyl-2-oxo-1,2-dihydroquinoline(4)-yl)-thionophosphoric acid esters and alkyl-O-alkyl(1-methyl2-oxo-1,2-dihydroquinoline-(4)-yl)thionophosphonic acid esters, which possess insecticidal properties.

Unified Siaies Paieni 1191 Lorenz et al.

Z-OXODIHYDROQUINOLINETHIONO- PHOSPHORIC (PHOSPHONIC) ACID ESTERSInventors: Walter iLorena, dWruppertal-Cronenbe r g; W Ingeborg Hammann, Cologne, Germany Assignee: Farbeniabriken BayerAktiengesellschaft, Leverkusen, Germany Filed: Jan. 5, 1971 Appl. No.:104,176

Foreign Application Priority Data Jan. 24, 1970 Germany ..P 20 03 141.8

US. Cl. 260/283 P, 260/289.4, 424/258 int. Cl. ..C07d 33/46 Field ofSearch ..260/283 P May 22,1973

Primary Examiner-Donald G. Daus Attomey-Burgess, Dinklage & Sprung [57]ABSTRACT 2-Oxodihydroquinolineihiono-phosphoric (-phosphonic) acidesters, i.e., 0,0-dialkyl-[l-methyl-2 0x0- 1 ,2-dihydroquinoline-(4 )-yl]-thiondphosphoric acid esters and a1kyl-O-alkyl[l-methyl-2-oxo-l,2-dihydroquinoline-(4)-yl]thionophosphonic acid esters, which possessinsecticidal properties.

6 Claims, No Drawings 2-OXODIHYDROQUINOLINETHIONO- PHOSPHORIC(PHOSPHONIC) ACID ESTERS The present invention relates to and has forits objects the provision of particular new 2-oxodihydroquinoline-thiono-phosphoric (-phosphonic) acid esters, i.e.,0,0-dialkyl-[1-methyl-2-oxo-l,2-dihydroquinoline-(4)-yl]-thionophosphoric acid esters and alkyl-O-alkyl[l-methyl-2-oxo-l ,2- dihydroquinoline-(4-)-yl]thionophosphonic acidesters, which possess insecticidal properties, active compositions inthe form of mixtures of said compounds with solid and liquid dispersiblecarrier vehicles, and methods for producing such compounds and for usingsuch compounds in a new way especially for combatting pests, e.g.insects, with other and further objects becoming apparent from a studyof the within specification and accompanying examples.

It is known from published Dutch Patent application No. 6,803,818 thatquinolinothionophosphoric (-phosphonic) acid esters exhibit aninsecticidal activity.

The present invention provides 2- oxodihydroquinoline-thionophosphoric(-phosphonic) in which R is a straight-chain or branched alkyl radicalwith one to six carbon atoms and R, is a straighbchain or branched alkylor alkoxy radical with one to six carbon atoms.

These compounds are distinguished by strong insecticidial properties.

The invention also provides a process for the production of a2-0xodihydroquinolinethionophosphoric (-phosphonic) acid ester of theformula ,(l) in which a dialkylthionophosphoric (phosphonic) acid esterha lide of the general formula:

Hal-P in which R and R have the above meanings, and Hal represents ahalogen atom,

is reached with l-methyl-Loxo-1,2-dihydro-4- hydroxyquinoline of theformula:

Gllz (lll) in the presence of an acid-binding agent or in the form of analkali metal salt, alkaline earth metal salt or ammonium salt.

Surprisingly, the new 2-oxodihydroquinolinethionophosphoric(-phosphonic) acid esters show a considerably better insecticidalactivity than the above- (III) The starting materials are definedgenerally by the formulas (II) and (Ill).

R and R stand preferably for a lower alkyl radical, e.g. an alkylradical with one to four carbon atoms, such as methyl, ethyl, isoorn-propyl, iso-, n-, tert.- or sec.-butyl, or (in the case of R,) a loweralkoxy radical, e.g. an alkoxy radical with one to four carbon atoms,and Hal stands preferably for a chlorine atom.

As examples of dialkylthiono-phosphoric (-phosphonic) acid ester halideswhich can be used as starting materials, there may be mentioned inparticular 0,0- dimethyl-, 0,0-diethyl-, 0,0-diisopropyl-, 0,0-di-tert.-(n-, sec.-)butyl-, 0-ethyl-0-iso-propyl-, O-isopropyl-O- butyl and0-methyl-0-isopropyl-thionophosphoric and O,P-methyl-, O,P-ethyl-,O,P-isopropyl-, O,P-tert.- butyl-, O-ethyl-P-isopropyl-,O-iso-propyl-P-ethyl-, O-butyl-P-methylandO-ethyl-P-butylthionophosphonic acid ester chloride or bromide.

' The dialkylthiono-phosphoric (-phosphonic) acid ester halides and thequinoline derivatives to be used as starting materials are described inthe literature and can be prepared by known methods.

The reaction may be carried out in the presence of a solvent which termincludes a mere diluent. For this purpose practically all inert organicsolvents are suitable. These include aliphatic and aromatic (optionallychlorinated) hydrocarbons, such as benzene, toluene, xylene, benzine,methylene chloride, chloroform, carbon tetrachloride, chlorobenzene;ethers, such as diethyl ether, dibutyl ether, dioxane; ketones, such asacetone, methylethyl ketone, methylisopropyl ketone, methylisobutylketone; nitriles, such as acetonitrile; and acid amides, especiallyN,N-dimethyl formamide; and the like.

As acid acceptors, all customary acid-binding agents can be used.Particularly good results have been obtained with alkali metalcarbonates and alcoholates, such as sodium or potassium carbonate,methylate or ethylate; aliphatic, aromatic or heterocyclic amines, forexample triethylamine, dimethylamine, dimethylaniline,dimethylbenzylamine and pyridine.

The reaction temperatures can be varied within a fairly wide range. Ingeneral, the reaction is carried out at about to 100 C, preferably atabout 35 to 50 C.

The reaction is, in general, carried out at normal pressure.

The starting components are generally used in equimolar amounts. Anexcess of one or other of the reactants seem to give no substantialadvantages.

The working up of the mixture may take place according to customarymethods. The substances according to the invention may be obtained incrystalline form and can be characterized by their melting points andelemental analyses.

The new 2-oxodihydroquinolinethiono-phosphoric (-phosphonic) acid estershave outstanding insecticidal properties, by reason by which they may beused for the control of noxious sucking and biting insects and Diptera,particularly in crop protection. In addition to this, they can also beused with success against hygiene pests and pests of stored products.

To the sucking insects there belong, in the main, aphids (Aphidae) suchas the green peach aphid (Myzus persicae), the bean aphid (Doralisfabae), the bird cherry aphid (Rhopalosiphum padi.), the pea aphid(Macrosiphum pisi) and the potato aphid (Macrosiphum solamfolii), thecurrant gall aphid (Cryptomyzus korschelti), the mealy apple aphid(Sappaphis mali), The mealy plum aphid (Hyalopterus arundinis) and thecherry black fly (Myzus cerasi); in addition, scales and mealybugs(Coccina), for example the oleander scale (Asphidiotus hederae) and thesoft scale (Lecanium hesperidum) as well as the grape mealybug(Pseudococcus maritimus); thrips (Thysanoptera), such asHercinothripsfemoralzlr, and bugs, for example the beet bug (Piesmaquadrata), the cotton bug (Dysdercus intermedius), the bed bug (Cimexlectularius), the assassin bug (Rhodnius prolixus) and Chagas bug(Triatoma infestans) and, further, cicadas, such as Euscelis bilobatusand Nephotettix bipunctatus; and the like.

In the case of the biting insects, above all there should be mentionedbutterfly caterpillars (Lepidoptera) such as the diamond-back moth(Plutella maculipennis), the gypsy moth (Lymantria dispar), thebrown-tail moth (Euproctis chrysorrhoea) and tent caterpillar(Malacosoma neustria); further, the cabbage moth (Mamestra brassicae)and the cutworm (Agrotis segetum), the large white butterfly (Pierisbrassicae), the small winter moth (Cheimarobia brumata), the green oaktortrix moth (Tortrix vin'dana), the fall armyworm (Laphygma frugiperda)and cotton worm (Prodenia litura), the ermine moth (Hyponomeutapadella), the Mediterranean flour moth (Ephestia kuhniella) and greaterwax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects are beetles (Coleoptera), forexample the granary weevil (Sitophilus granarius Calandra granaria), theC010- rado beetle (Leptinotarsa decemlineata), the dock beetle(Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), theblossom beetle (Meligethes aeneus), the raspberry beetle (Byturustomentosus), the bean weevil (Bruchidius Acanthoscelides obtectus), theleather beetle (Dermestes frischi), the khapra beetle (Trogodermagranarium), the flour beetle (Tribolium castaneum), the northern cornbillbug (Calandra or Sitophilus zeamais), the drugstore beetle(Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and thesaw-toothed grain beetle (Oryzaephilus surinamensis), and also speciesliving in the soil, for example wireworms (Agn'otes spec.) and larvae ofthe cockchafer (Melolontha melolontha); cockroaches, such as the Germancockroach (Blattella germanica), American cockroach (Periplanetaamericana), Madeira cockroach (Leucophaea or Rhyparobia maderae),Oriental cockroach (Blatta orientalis), the giant cockroach (Blaberusgiganteus) and the black giant cockroach (Blaberusfuscus) as well asHenschoutedenia flexivitta; further, Orthoptera, for example the housecricket (Acheta domesticus); termites such as the eastern subterraneantermite (Reticulitermes flavipes) and Hymenoptera such as ants, forexample the garden ant (Lasius niger); and the like.

The Diptera comprise essentially the flies, such as the vinegar fly(Drosophila melanogaster), the Mediterranean fruit fly (Ceratitiscapitata), the house fly (Musca domestica), the little house fly (Fanniacanicularis), the black blow fly (Phormia aegina) and bluebottle fly(Calliphora erthyrocephala) as well as the stable fly (Stomoxyscalcitrans); further, gnats, for example mosquitoes such as the yellowfever mosquito (Aedes aegypti), the northern house mosquito (Culexpipiens) and the malaria mosquito (Anopheles stephensi); and the like.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents or extenders of the typeusable in conventional pesticide formulations or compositions, e. g.conventional pesticide dispersible carrier vehicles such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders,pastes, soluble powders, dusting agents, granules, etc. These areprepared in known manner, for instance by extending the active compoundswith conventional pesticide dispersible liquid diluent carriers and/ordispersible solid carriers optionally with the use of carrier vehicleassistants, e.g. conventional pesticide surface-active agents, includingemulsifying agents and/or dispersing agents, whereby, for example, inthe case where water is used as diluent, organic solvents may be addedas auxiliary solvents. The following may be chiefly considered for useas conventional carrier vehicles for this purpose: inert dispersibleliquid diluent carriers, including inert organic solvents, such asaromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.),halogenated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine,etc.), esters, ether-alcohols, (e.g. glycol monomethyl ether, etc.),amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc.) and/or water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate,talc, kieselguhr, etc.), and ground synthetic minerals (e.g. highlydispersed silicic acid, silicates, e.g. alkali silicates, etc.), whereasthe following may be chiefly considered for use as conventional carriervehicle assistants, e.g. surface-active agents, for this purpose:emulsifying agents, such as non-ionic and/or anionic emulsifying agents(e.g. polyethylene oxide esters of fatty acids, polyethylene oxideethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., andespecially alkyl arylpolyglycol ethers, magnesium stearate, sodiumoleate, etc.); and/or dispersing agents such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other insecticides, oracaricides, rodenticides, fungicides, herbicides, bactericides, etc., ifdesired, or in the form of particular dosage preparations for specificapplication made therefrom, such as solutions, emulsions, suspensions,powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.1-95 percent byweight, and preferably 05-90 percent by weight, of the mixture, whereascarrier composition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.0001- percent,preferably 0.1-1 percent, by weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprise mixtures ofa conventional dispersible carrier vehicle such as (l) a dispersibleinert finely divided carrier solid, and/or (2) a dispersible carrierliquid such as an inert organic solvent and/or water preferablyincluding a surface-active effective amount of a carrier vehicleassistant, e.g. a surface-active agent, such as an emulsifying agentand- /or a dispersing agent, and an amount of the active compound whichis effective for the purpose in question and which is generally betweenabout 0.00001-95 percent, and preferably 0.01-95 percent, by weight ofthe mixture.

The active compounds can also beused in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the seame, via very effective atomizing equipment, in finelydivided form, e,g, average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amount only up to about 1 quartlacre, preferably 2--16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about to about 95 percent by weight of activecompound or even the 100 percent active substance alone, e.g. about20-100 percent by weight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects, and moreparticularly methods of combating insects which comprises applying to atleast one of correspon-dingly (a) such insects, and (b) their habitat,i.e., the locus to be protected, a correspondingly combative or toxicamount, i.e. an insecticidally effective amount, of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, squirting, sprinkling,pouring, fumigating, dressing,

incrusting and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

EXAMPLE 1 Phaedon larvae test (plant-damaging insects) Solvent: 3 partsby weight acetone Emulsifier: 1 part by weight alkylaryl polyglycolether To produce a suitable preparation of active com pound, 1 part byweight of the active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier, and the concentrate isdiluted with water to be desired concen-tration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dripping wet and then infested with mustardbeetle larvae (Phaedon cochleariae).

After the specified periods of time, the degree of destruction isdetermined as a percentage: 100 percent means that all the beetle larvaeare killed 0 percent means that none of the beetle larvae are killed.

The active compounds, the concentration of the active compound, thetimes of evaluation and the results can be seen from the following Table1.

S ll

TABLE 1 Continued (Phaedon larvae test) Concentration of Degree ofactivecompound destruction in percent in percent Active compound after 3days (4) CH3 S 0.01 100 P-O C H O EXAMPLE 2 Myzus test (contact action)Solvent: 3 parts by weight acetone Emulsifier: 1 part by weightalkylaryl polyglycol ether To produce a suitable preparation of activecompound 1 part by weight of the active compound is mixed with thestated amount of solvent containing the stated amount of emulsifier andthe concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested withpeach aphids (Myzus persicae) are sprayed with the preparation of theactive compound until dripping wet.

After the specified periods of time, the degree of destruction isdetermined as a percentage: 100 percent means that all the aphids arekilled whereas 0 percent means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 2.

TABLE 2 (Ill:

TABLE 2 -Continued (Myzus test.)

Concentration llogrcc of olactivc destruction compound in pcrccnt.Actlvc compound in pcrccnt :iltcr 1 day S l). t ion H 0. 0i 100 (C1HO)1P(\) 0.001 100 0' \N/ (EH3 C H 0. i 100 2 0. 01 100 P-O 0. 001 55 I0111 0 CH S 0. 1 100 0. 01 100 PO 0. 001 I 0 1150 O: N 41H;

EXAMPLE 3 H o-mocn 2 196 g (1 mole) of the sodium salt ofl-methyl-2-oxol,2-dihydro-4-hydroxyquinoline are dissolved in 300 ml ofdimethyl formamide. To this solution there are added dropwise, withcooling, 160.5 g (1 mole) 0,0-dimethylthionophosphoric acid chloride.The temperature of the mixture should not exceed 35 C. After stirringfor two hours at room temperature, the mixture is poured into water, theseparated oil is taken up in benzene, the benzene solution is washedwith 2N sodium hydroxide solution and water and dried over sodiumsulfate. The deep-brown reaction mixture is then repeatedly treated withanimal charcoal and bleaching earth. After the solvent has beendistilled ofi, an oil remains behind which slowly crystallizes. Forfurther purification of the product, it is dissolved in ether, a browngrease remaining undissolved. After the ether is distilled off, 51 g(17.1 percent of the theory) of 0,0- dimethyl-[ l-methyl-2-oxol,2-dihydroquinoline-(4 yl]-thionophosphoric acid ester are obtained asyellow powder of the melting point 62 C.

a. 88 g (0.5 mole) of l-methyl-Z-oxo-1,2-dihydro-4- hydroxyquinoline aredissolved in 300 m1 of dimethyl formamide. After addition of 82.5 g (0.6mole) of ground potassium carbonate, the mixture is heated to 50 C forhalf an hour, with stirring; at this temperature, 94 g (0.5 mole) of0,0-diethylthionophosphoric acid ester chloride are added dropwise. Amildly exothermic reaction occurs. To complete the reaction, the mixtureis stirred for further hour at room temperature, and it is then pouredinto water. The separated oil is taken up in chloroform, the chloroformsolution is first washed repeatedly with water in order to remove thedimethyl formamide, then with a 2N solution of sodium hydroxide and,finally, again treated with water. After drying over sodium sulfate, thechloroform solution is repeatedly purified with animal charcoal andbleaching earth. After the solvent is distilled off, 60 g (36.7 percentof the theory) of 0,0-diethyl-[ l -methyl-2-oxo-l ,2-dihydroquinoline-(4)-yl]-thionophosphoric acid ester are obtained in theform of yellow, coarse crystals which are washed with petroleum etherand then melt at 64 C.

Analysis: N P g S Calculated for C H NOJS 4.28%; 9.46%; 9.79%;(molecular weight 327.3):

Found: 4.33%; 9.88%; 9.99%.

b. 88 g (0.5 mole) of 1-methyl-2-oxo-l,2-dihydro-4- hydroxyquinoline aresuspended in 500 ml methylethyl ketone. After introduction of 75 g (0.55mole) of ground potassium carbonate and 1 g of copper powder, themixture is heated to 60 to 70 C for half an hour, with stirring: at thistemperature there are added to it 94 g (0.5 mole) of0,0-diethylthionophosphoric acid ester chloride, the mixture is thenheated to 90 C for 2 hours, allowed to cool; the reaction mixture ispoured into much water, and the separated oil is taken up in benzene.The working up takes place in the manner described above. After thebenzene is distilled off, 109 g of crude product are obtained. It isdissolved in an ether/petroleum ether mixture (1:15 and the solution iscooled to C, the 0,0-diethyl-[l-methyl-2 -oxol,2-dihydroquinoline-(4)-yll-thionophosphoric acid ester crystallizingout in yellow, coarse crystals of m.p. 64 C. The yield is 27.8 percentof the theory.

Analysis: N P S Calculated for C l-L NOJS (molecular weight 327.3):4.28%; 9.46%; 9.79%; Found: 4.21%; 9.57%; 10.09%.

EXAMPLE 5 W l 'CQH Analogously with Example 4a, by reaction withethylthionophosphonic acid O-ethyl ester chloride there is obtainedethyl-0-ethyl-[ l-methyl2-oxo-l ,2-dihydroquinoline-(4)-yl]-thionophosphonic acid ester in the form ofyellow crystals of the melting point 58 C. The yield is 27.3 percent ofthe theory.

Analysis: N P I S 7 Calculated for C H NO PS (molecular weight 311.3):4.50%; 9.98%; 10.30%; Found: 4.63%; 10.1 1%; 10.49%.

EXAMPLE 6 0 Calls In manner analogous with that described in Example 4a,by reaction with methylthionophosphonic acid 0- ethyl ester chloridethere is obtained methyl-O-ethyll-methy1-2-oxo-l ,2-dihydroquinoline-(4)-yl]- thionophosphonic acid ester in the form of beigecolored crystalsof the melting point to 122 C from ethyl acetate/petroleum ether.

The yield is 61.7 percent of the theory.

Analysis: N P S Calculated for C H NO PS (molecular weight 297.2):4.72%; 10.45%; 10.80%; Found: 493%; 10.41%; 10.73%.

3. Compound according to claim 1 wherein such- 0,0-dimethyl-[l-methyl-Z-oxo-l ,2

compound is dihydroquinoline-(4)-yl]-thionophosphoric acid ester of theformula l CH3 4. Compound according to claim 1 wherein such compound is0,0-diethyl[ 1-methyl-2-oxol ,2-dihydroquinoline-(4)-yl]-thionophosphoric acid ester of the formula NCH: (1)

12 5. Compound according to claim 1 wherein such compound isethyl-0-ethyl-[ l-methyl-2-oxo-l ,2-dihydroquinoline-(4)-yl]-thionophosphonic acid ester of the formula 6.Compound according to claim 1 wherein such compound ismethyl-0-ethyl-[l-methyl-2-oxo-l,2-dihydroquinoline-(4)-yl]-thionophosphonic acid ester of the formula

2. Compound according to claim 1 in which R and R1 each has one to fourcarbon atoms.
 3. Compound according to claim 1 wherein such compound is0,0-dimethyl-(1-methyl-2-oxo-1,2-dihydroquinoline-(4)-yl)-thionophosphoric acid esterof the formula
 4. Compound according to claim 1 wherein such compound is0,0-diethyl(1-methyl-2-oxo-1,2-dihydroquinoline-(4)-yl)-thionophosphoricacid ester of the formula
 5. Compound according to claim 1 wherein suchcompound isethyl-0-ethyl-(1-methyl-2-oxo-1,2-dihydroquinoline-(4)-yl)-thionophosphonicacid ester of the formula
 6. Compound according to claim 1 wherein suchcompound ismethyl-0-ethyl-(1-methyl-2-oxo-1,2-dihydroquinoline-(4)-yl)-thionophosphonicacid ester of the formula